Electrokinetic treatment of environmental matrices. Contaminants removal and phosphorus recovery

There is a need to develop viable techniques for removal and recovery organic and inorganic compounds from environmental matrices, due to their ecotoxicity, regulatory obligations or potential supplies as secondary materials. In this dissertation, electro –removal and –recovery techniques were applied to five different contaminated environmental matrices aiming phosphorus (P) recovery and/or contaminants removal. In a first phase, the electrokinetic process (EK) was carried out in soils for (i) metalloids and (ii) organic contaminants (OCs) removal. In the case of As and Sb mine contaminated soil, the EK process was additionally coupled with phytotechnologies. In a second phase, the electrodialytic process (ED) was applied to wastes aiming P recovery and simultaneous removal of (iii) toxins from membrane concentrate, (iv) heavy metals from sewage sludge ash (SSA), and (v) OCs from sewage sludge (SS). EK enhanced phytoremediation showed to be viable for the remediation of soils contaminated with metalloids, as although remediation was low, it combines advantages of both technologies while allowing site management. EK also proved to be an effective remediation technology for the removal and degradation of emerging OCs from two types of soil. Aiming P recovery and contaminants removal, different ED cell set-ups were tested. For the membrane concentrates, the best P recovery was achieved in a three compartment (3c) cell, but the highest toxin removal was obtained in a two compartment (2c) cell, placing the matrix in the cathode end. In the case of SSA the best approach for simultaneous P recovery and heavy metals removal was to use a 2c-cell placing the matrix in the anode end. However, for simultaneous P recovery and OCs removal, SS should be placed in the cathode end, in a 2c-cell. Overall, the data support that the selection of the cell design should be done case-by-case.

Les neutrophiles ne sont pas résistants aux glucocorticoides

Les neutrophiles sont généralement considérés résistants aux glucocorticoïdes. Cependant, peu d’études comparant l’effet de ces drogues sur les neutrophiles et les autres leucocytes sanguins (monocytes, lymphocytes et éosinophiles) ont été rapportées. Dans notre étude, nous avons évalué la réponse aux glucocorticoïdes de ces deux populations cellulaires chez le cheval et l’homme. Les cellules, préalablement isolées du sang de 6 chevaux et 4 sujets humains sains, ont été incubées pendant 5 h en présence de lipopolysaccharide (LPS; 100 ng/mL) seul ou combiné avec de l’hydrocortisone, de la prednisolone ou de la dexaméthasone (10-8M et 10-6M). L’expression d’ARNm pour l’IL-1β, le TNF-α, l’IL-8, la glutamine synthétase et le récepteur α des glucocorticoïdes (GR-α) a été quantifiée par qPCR. Les neutrophiles équins ont également été incubés pendant 20 h en présence de ces 3 glucocorticoïdes et la survie cellulaire a été évaluée par cytométrie de flux et microscopie optique. Nous avons démontré que les glucocorticoïdes inhibaient l’expression des gènes pro-inflammatoires induite par le LPS pour les deux populations cellulaires chez les deux espèces étudiées. L’expression de la glutamine synthétase était également significativement augmentée par les glucocorticoïdes chez les neutrophiles et les autres leucocytes sanguins équins. De manière générale, l’intensité de la réponse aux glucocorticoïdes s’est avérée similaire dans les 2 populations leucocytaires et chez les deux espèces. Les glucocorticoïdes augmentaient également la survie des neutrophiles équins, phénomène également rapporté dans d’autres espèces. Ainsi, les glucococorticoïdes exercent des effets d’intensité comparable sur les neutrophiles et les autres leucocytes sanguins. Nous spéculons que la faible réponse à la corticothérapie observée lors de maladies inflammatoires chroniques neutrophiliques comme l’asthme sévère ou la Maladie Pulmonaire Obstructive Chronique (MPOC) ne s’explique pas par une corticorésistance intrinsèque des neutrophiles.

Investigations on Photoconductivity and Electrical Switiching in Selected Chalcogenide Glasses

In this thesis, we present the results of our investigations on the photoconducting and electrical switching properties of selected chalcogenide glass systems. We have used XRD and X-ray photoelectron spectroscopy (XPS) analysis for confinuing the amorphous nature of these materials and for confirming their constituents respectively.Photoconductivity is the enhancement in electrical conductivity of materials brought about by the motion of charge carriers excited by absorbed radiation. The phenomenon involves absorption, photogeneration, recombination and transport processes and it gives good insight into the density of states in the energy gap of solids due to the presence of impurities and lattice defects. Photoconductivity measurements lead to the determination of such important parameters as quantum efficiency, photosensiti\'ity, spectral sensitivity and carrier lifetime. Extensive research work on photoconducting properties of amorphous semiconductors has resulted in the development of a variety of very sensitive photodetectors. Photoconductors are finding newer and newer uses eyery day. CdS, CdSe. Sb2S3, Se, ZnO etc, are typical photoconducting materials which are used in devices like vidicons, light amplifiers, xerography equipment etc.Electrical switching is another interesting and important property possessed by several Te based chalcogenides. Switching is the rapid and reversible transition between a highly resistive OFF state, driven by an external electric field and characterized by a threshold voltage, and a low resistivity ON state, Switching can be either threshold type or memory type. The phenomenon of switching could find applications in areas like infonnation storage, electrical power control etc. Investigations on electrical switching in chalcogenide glasses help in understanding the mechanism of switching which is necessary to select and modify materials for specific switching applications.Analysis of XRD pattern gives no further infonuation about amorphous materials than revealing their disordered structure whereas x-ray photoelectron spectroscopy,XPS) provides information about the different constituents present in the material. Also it gives binding energies (b.e.) of an element in different compounds and hence b.e. shift from the elemental form.Our investigations have been concentrated on the bulk glasses, Ge-In-Se, Ge-Bi-Se and As-Sb-Se for photoconductivity measurements and In-Te for electrical switching. The photoconducting properties of Ge-Sb-Se thin films prepared by sputtering technique have also been studied. The bulk glasses for the present investigations are prepared by the melt quenching technique and are annealed for half an hour at temperatures just below their respective glass transition temperatures. The dependence of photoconducting propenies on composition and temperature are investigated in each system. The electrical switching characteristics of In-Te system are also studied with different compositions and by varying the temperature.

Vacancy-assisted domain-growth in asymmetric binary alloys: A Monte Carlo Study

A Monte Carlo simulation study of the vacancy-assisted domain growth in asymmetric binary alloys is presented. The system is modeled using a three-state ABV Hamiltonian which includes an asymmetry term. Our simulated system is a stoichiometric two-dimensional binary alloy with a single vacancy which evolves according to the vacancy-atom exchange mechanism. We obtain that, compared to the symmetric case, the ordering process slows down dramatically. Concerning the asymptotic behavior it is algebraic and characterized by the Allen-Cahn growth exponent x51/2. The late stages of the evolution are preceded by a transient regime strongly affected by both the temperature and the degree of asymmetry of the alloy. The results are discussed and compared to those obtained for the symmetric case.

Electronic couplings and on-site energies for hole transfer in DNA: systematic quantum mechanical/molecular dynamic study

The electron hole transfer (HT) properties of DNA are substantially affected by thermal fluctuations of the π stack structure. Depending on the mutual position of neighboring nucleobases, electronic coupling V may change by several orders of magnitude. In the present paper, we report the results of systematic QM/molecular dynamic (MD) calculations of the electronic couplings and on-site energies for the hole transfer. Based on 15 ns MD trajectories for several DNA oligomers, we calculate the average coupling squares 〈 V2 〉 and the energies of basepair triplets X G+ Y and X A+ Y, where X, Y=G, A, T, and C. For each of the 32 systems, 15 000 conformations separated by 1 ps are considered. The three-state generalized Mulliken-Hush method is used to derive electronic couplings for HT between neighboring basepairs. The adiabatic energies and dipole moment matrix elements are computed within the INDO/S method. We compare the rms values of V with the couplings estimated for the idealized B -DNA structure and show that in several important cases the couplings calculated for the idealized B -DNA structure are considerably underestimated. The rms values for intrastrand couplings G-G, A-A, G-A, and A-G are found to be similar, ∼0.07 eV, while the interstrand couplings are quite different. The energies of hole states G+ and A+ in the stack depend on the nature of the neighboring pairs. The X G+ Y are by 0.5 eV more stable than X A+ Y. The thermal fluctuations of the DNA structure facilitate the HT process from guanine to adenine. The tabulated couplings and on-site energies can be used as reference parameters in theoretical and computational studies of HT processes in DNA

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states (1(2)A', 2(2)A', 1(2)A '') of the C2Br radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, R-CC = 1.2621 angstrom, R-CBr = 1.7967 angstrom, < CCBr 156.1 degrees, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C2F and C2Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Sigma, Pi(1/2), Pi(3/2) vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5K have been calculated for the (CCBr)-C-12-C-12-Br-79 isotopomer, to an upper limit of 2000 cm(-1), using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.

Secondary structure prediction with support vector machines

Motivation: A new method that uses support vector machines (SVMs) to predict protein secondary structure is described and evaluated. The study is designed to develop a reliable prediction method using an alternative technique and to investigate the applicability of SVMs to this type of bioinformatics problem. Methods: Binary SVMs are trained to discriminate between two structural classes. The binary classifiers are combined in several ways to predict multi-class secondary structure. Results: The average three-state prediction accuracy per protein (Q3) is estimated by cross-validation to be 77.07 ± 0.26% with a segment overlap (Sov) score of 73.32 ± 0.39%. The SVM performs similarly to the 'state-of-the-art' PSIPRED prediction method on a non-homologous test set of 121 proteins despite being trained on substantially fewer examples. A simple consensus of the SVM, PSIPRED and PROFsec achieves significantly higher prediction accuracy than the individual methods. Availability: The SVM classifier is available from the authors. Work is in progress to make the method available on-line and to integrate the SVM predictions into the PSIPRED server.

Interpreting Differential Temperature Trends at the Surface and in the Lower Troposphere

Estimated global-scale temperature trends at Earth's surface (as recorded by thermometers) and in the lower troposphere (as monitored by satellites) diverge by up to 0.14°C per decade over the period 1979 to 1998. Accounting for differences in the spatial coverage of satellite and surface measurements reduces this differential, but still leaves a statistically significant residual of roughly 0.1°C per decade. Natural internal climate variability alone, as simulated in three state-of-the-art coupled atmosphere-ocean models, cannot completely explain this residual trend difference. A model forced by a combination of anthropogenic factors and volcanic aerosols yields surface-troposphere temperature trend differences closest to those observed.

A new species of Lauromacromia (Odonata: Corduliidae) from Southeastern Brazil, with a cladistic analysis of the genus and comments on Neotropical dragonfly biogeography

Lauromacromia melanica sp. nov. from Conceicao da Barra municipality, Espirito Santo State, Brazil, is described and illustrated based on two males (both in MNRJ n degrees 135). The new species is similar to L. picinguaba differing from it mainly by the absence of pale spots on S3-6 and by the ellipsoid shape of metepisternal pale stripe. A key for males of all species of the genus is provided. A cladistic analysis encompassing 43 external morphological male characters carried out in two distinct procedures, the first with all characters unordered and the second with two or three state characters ordered. The unordered analysis generated only one most-parsimonious tree (66 steps of length, CI = 0.69, RI = 0.62). The hypothesis of monophyly of Lauromacromia is supported and includes three groups, one formed by the Atlantic Forest species (L. melanica sp. nov. + L. picinguaba), and another by the Cerrado species (L. flaviae + (L. bedei + L. luismoojeni)), and L. dubitalis, positioned in polytomy with these two groups. The ordered analysis also generated only one most-parsimonious tree (68 steps of length, CI = 0.70, RI = 0.67), which maintained the monophyly of Lauromacromia but L. dubitalis positioned basally as sister-group to the Atlantic Forest + Cerrado species groups. The geographic distribution of Lauromacromia is updated with a new record of L. luismoojeni based on one adult male (Brazil: Mato Grosso do Sul State) and probable first Brazilian records for L. dubitalis (Amazonas and Para States) based on two larvae. A vicariance hypothesis is proposed to explain spatial evolution of Lauromacromia, and based on current biogeographical classifications we consider Gomphomacromia and Rialla apart from Neotropical biota. Some aspects of biology and ecology of Lauromacromia are also discussed.

Effect of the anti-neoplastic drug doxorubicin on XPD-mutated DNA repair-deficient human cells

Doxorubicin (DOX), a member of the anthracycline group, is a widely used drug in cancer therapy. The mechanisms of DOX action include topoisomerase II-poisoning, free radical release, DNA adducts and interstrand cross-link (ICL) formation. Nucleotide excision repair(NER) is involved in the removal of helix-distorting lesions and chemical adducts, however, little is known about the response of NER-deficient cell lines to anti-tumoral drugs like DOX. Wild type and XPD-mutated cells, harbouring mutations in different regions of this gene and leading to XP-D, XP/CS or TTD diseases, were treated with this drug and analyzed for cell cycle arrest and DNA damage by comet assay. The formation of DSBs was also investigated by determination of gamma H2AX foci. Our results indicate that all three NER-deficient cell lines tested are more sensitive to DOX treatment, when compared to wild type cells or XP cells complemented by the wild type XPD cDNA, suggesting that NER is involved in the removal of DOX-induced lesions. The cell cycle analysis showed the characteristic G2 arrest in repair-proficient MRC5 cell line after DOX treatment, whereas the repair-deficient cell lines presented significant increase in sub-G1 fraction. The NER-deficient cell lines do not show different patterns of DNA damage formation as assayed by comet assay and phosphorylated H2AX foci formation. Knock-down of topoisomerase II alpha with siRNA leads to increased survival in both MRC5 and XP cells, however, XP cell line still remained significantly more sensitive to the treatment by DOX. Our study suggests that the enhanced sensitivity is due to DOX-induced DNA damage that is subject to NER, as we observed decreased unscheduled DNA synthesis in XP-deficient cells upon DOX treatment. Furthermore, the complementation of the XPD-function abolished the observed sensitivity at lower DOX concentrations, suggesting that the XPD helicase activity is involved in the repair of DOX-induced lesions. (C) 2009 Elsevier B.V. All rights reserved.

Valores organizacionais: uma análise no contexto educacional

This research¿s main goal was to analyze the existing relationship between both environmental and organizational values from three State Schools located in the city of Curitiba. These are: Protásio de Carvalho School, Guaíra School and Rio Branco School. At a theoretical empirical reference, an environmental approach has been performed, followed by aspects regarding organizational values, including the discussion on the theme of organizational culture, and, finally, a study on the prevalent values in public educational institutions. The method that best features this research is a comparative case report, with the use of multiple sources of evidence. Secondary data in order to identify the environmental values has been obtained through references of two of the most important newspapers in the State of Paraná, reports published by the State¿s Secretary of Education, publications from the State¿s Teachers Union and through the Educational Legislation in both Federal and State levels. The organizational values have been identified from primary data obtained through semi-structured interviews, performed with the School Principals and through questionnaires distributed to the School Principals and Teachers. The analysis over this data has been carried out in a descriptive-qualitative way by using both documentary and content analysis techniques. The database revealed that there are a few consistencies between environmental and organizational values, in a way that certain values identified in society and in the Government are, several times, more congruent with the values identified in the group of School Principals, whereas the values identified in the Teacher¿s Union have a higher consistency with the prevalent values in the group of teachers. At schools, mainly in the group of teachers, there¿s a noticeable refraction towards actions promoted by the government, and a certain skepticism towards actions promoted by the Teacher¿s Union. The student¿s education is given a higher value than one¿s cognitive education, in the work atmosphere as much as in the organizations; the Society has been gradually taking the responsibility regarding public education, with the support of school boards, teachers, and even of the Government, at a time when teachers, unlike the Society and the Government, appear to give very little value to their own profession.

Características dos serviços de auditoria interna em empresas estatais: o caso das empresas do estado do Ceará

o objetivo desta pesquisa foi analisar, através de um estudo exploratório, o funcionamento dos serviços de Auditoria Interna e conhecer as práticas atualmente empre gadas em três empresas estatais do Estado do Ceará, à luz de urna comparaçao com os fundamentos teóricos sobre Interna. Auditoria "Na revisão da literatura apresenta-se a perspectiva histórica, evidenciando o surgimento e desenvolvime~ to da Auditoria Interna, destacando-se principalmente os aspectos mais relevant"es. A seguir, são apresentadas consideraçoes gerais sobre Auditoria Interna em empresas estatais. A partir dessa revisão foi possível desenvolver um plano de referência para ser utilizado nesta pesquisa. A metodologia adotada neste trabalho foi o es tudo de caso, e as razoes de seu emprego são justificadas além das limitações desse tipo de estudo exploratório. , Entrevistas, utilizando questionários, compos tos em sua maioria de questões abertas, permitiram urna descrição dos serviços de Auditoria Interna desenvolvidos pelas empresas estatais estaduais, bem corno as informações obtidas no Departamento de Auditoria Geral do Estado, além da Comissão de Auditoria Administrativa do Estado do Ceará.Os resultados obtidos possibilitaram uma análise sobre as características dos serviços de Auditoria Interna projetados pelas empresas estatais estaduais, bem como sobre o funcionamento desses serviços e as práticas desenvol vidas pelas empresas pesquisadas. Finalmente, comparando-se os resultados da pesquisa de campo com a literatura existente, pode-se chegar a algumas conclusões importantes, como também formular recomendações para o Governo Estadual e para as empresas pesquisadas, além de algumas sugestões para pesquisas futuras.

Três ensaios sobre o mercado de trabalho no Brasil

Esta tese é composta por três artigos e uma nota, sendo um em cada capítulo. Todos os capítulos enquadram-se na área de Microeconomia Aplicada e Economia do Trabalho. O primeiro artigo estende o modelo tradicional de decomposição das flutuações na taxa de desemprego de Shimer (2012), separando o emprego formal do informal. Com essa modificação, os principais resultados da metodologia se alteram e conclui-se que os principais fatores para a queda do desemprego na última década foram (i) a queda na taxa de participação, principalmente pela menor entrada na força de trabalho; (ii) o aumento da formalização, atingido tanto pelo aumento da probabilidade de encontrar um trabalho formal quanto pela probabilidade de deixar a condição de empregado formal. O segundo capítulo apresenta estimativas para o retorno à educação no Brasil, utilizando uma nova metodologia que não necessita de variáveis de exclusão. A vantagem do método em relação a abordagens que utilizam variáveis instrumentais é a de permitir avaliar o retorno médio para todos os trabalhadores (e não somente os afetados pelos instrumentos) e em qualquer instante do tempo. Face aos resultados, concluímos as estimativas via MQO subestimam o retorno médio. Discute-se possíveis explicações para esse fenômeno. O terceiro artigo trata da terceirização da mão de obra no Brasil. Mais especificamente, mede-se o diferencial de salários entre os trabalhadores terceirizados e os contratados diretamente. Os resultados de uma comparação não condicional indicam que os terceirizados têm salário médio 17% menor no período 2007 a 2012. Porém, com estimativas que levam em conta o efeito fixo de cada trabalhador, esse diferencial cai para 3,0%. Além disso, o diferencial é bastante heterogêneo entre os tipos de serviços: aqueles que utilizam trabalhadores de baixa qualificação apresentam salário menores, enquanto nas ocupações de maior qualificação os terceirizados têm salários iguais ou maiores do que os diretamente contratados. Mais ainda, as evidencias apontam para a diminuição do diferencial ao longo do tempo no período analisado. Finalmente, a nota que encerra a tese documenta dois aspectos relevantes e pouco conhecidos da Pesquisa Mensal de Emprego do IBGE que podem levar a resultados imprecisos nas pesquisas que utilizam esse painel se não forem tratados adequadamente.

Repercussão geral e súmula vinculante: os efeitos no controle difuso

Brazil since its first republican constitution has adopted systems of laws control. The review activity was given to three state powers or functions state, Executive, Legislative and Judiciary. However, it appears that in the country along the constitutional history, has stood considerably the jurisdictional control of the most important control. Initially, back in 1891, Brazil adopted the jurisdictional control of diffuse from U.S, whose role in monitoring of standards is delivered to all organs of the judiciary, which may face a case, put on trial, ascertain whether or not the possibility of applying a law, removing its impact in case of unconstitutionality. In 1969, entered in the second legal model of judicial review, the concentrated control of constitutionality, whose inspiration comes from the positivist theory of Hans Kelsen, and was adopted by the Austrian Constitution of 1920. According to the abstract control the supervision of law is given to a Court or Constitutional Court, responsible for the analysis of the legal constitutionality independent of its application to a specific case. In Brazil the role of concentrated control was handed over exclusively to the Supreme Court, which serves as the Constitutional Court, which accumulates that function with other constitutionally provided jurisdiction. Throughout this period, from 1891 until today, Brazil has maintained a dual system of judicial control of legal constitutionality, where they coexist and harmonize the diffuse control exercised by any organ of the Judiciary, and concentrated control of competence the Supreme Court. However, one must recognize that with the advent of the Federal Constitution of 1988, the concentrated control has emerged on the national stage due to two important factors: the expansion of the legal capacity to sue and the inclusion of other ways control, besides the already known Direct Claim of Unconstitutionality. This concentrated control and projection of the Supreme Court s attempt to become a true constitutional court, led to a relative weakening of diffuse control even when performed by the Brazilian Constitutional Court. In order to become a true constitutional court, all decisions handed down by the Supreme in the exercise of constitutional jurisdiction should have the same weight and the same measure, or at least bring improvement to similar effects, once is the responsible for the final word when it comes to constitutional interpretation. Thus, the writs of certiorari and stare decisis were responsible for profound changes in the diffuse control, allowing the Supreme Court can strengthen its decisions even in the diffuse control. These two institutions have substantially changed the legal status of diffuse control, allowing an extension of the effects of decisions handed down by the Supreme Court, so that you can no longer be said that the effects of this control to restrict the disputing parties in the process

CREATION: técnica de criatividade para geração de ideias de novos produtos

Creativity is a skill found in all individuals and one of the strategies used to intensify it is through the application of creativity techniques. In order to propose a new technique for generating new crafts product ideas, this dissertation, which is part of a research project of the Federal University of Rio Grande do Norte, through action research, intervened in three state communities artisans - Lajes Pintada, Massaranduba and Vera Cruz - to develop the artisans creative potential. Based on the techniques studied in the literature, we selected three techniques for interventions, composing two dynamics - one to improve features and functionalities of existing products, with the technique of SCAMPER; and the other to generate ideas for creating new products, with techniques Listing and Random Words / Figures. These latter techniques were not satisfactory in its objective by presenting constraints, not covered in the description, for the participant group. Thus, it was necessary to propose a new technique for the same purpose, the technique CREATION Clarify technique, Realized creativity, Explain, Apply for word, Think fast, Interpret, Organize ideas, Now evaluate, composed of twelve steps. To use the new technique requires that it be used by a dynamic that takes into account three phases: Planning, Application and Analysis. In the new technique application were generated around 30 ideas, regarded as new, in six sessions, from test pilot to interventions in artisans communities